CN1346833A - Process for chemical modifying surface of emulsion polymer particles - Google Patents

Abstract

Processes for chemically-modifying the surface of an emulsion polymer particle are provided which include providing an aqueous emulsion polymer, a monomer at a level of at least 0.5% by weight based on the weight of the emulsion polymer and a surface-modifying chemical capable of bonding with the monomer, under conditions where there is no substantial polymerization of the monomer, and then reducing the level of the monomer by at least 50%.

Description

The chemical modification method of surface of emulsion polymer particles

The present invention relates to the chemical modification method of surface of emulsion polymer particles and the emulsion polymer particle of surface modification.More specifically, the chemical modification method of the surface of emulsion polymer particles that increases of the surface concn that provides than existing method of its surface concns that relate on the particle and modified chemical product surface bonding.

Usually wish to make specific component or functional group's (being called " surface modification chemical " herein) Chemical bond to arrive the surface of polymkeric substance.For example, wish to make acid functional group be connected to surface of emulsion polymer particles to help the stability of polymer beads in water.This to a certain extent can be by in other monomeric polymeric part, in the whole process of other monomer polymerization, make the acidiferous monomer polymerization realize that the polymerization conduct of described acidiferous monomer is used to form the outer field monomeric polymeric part of multistage polymkeric substance, or its certain combination.But, in the part emulsion polymer particle that does not need, also do not wish to have acidiferous monomer, introduce acidiferous monomer and be not only costliness and waste, and caused performance issue, as reduced water tolerance and erosion resistance, increased water sensitivity.In addition, in down one deck or skin, provide the trial with the modified chemical product of surface bonding usually in water-bearing media, to stay not introducing or remaining surface modification chemical.This remaining surface modification chemical can further aggravate the water sensitivity of system.

Even, form the internal layer of the in fact penetrable polymkeric substance of outer field polymer chain, rather than form independently outer when people successfully introduce the surface modification chemical at the skin of polymer beads.This penetrating that forms outer field polymer chain is embedded in some surface modification chemical (described chemical is the part of polymer chain) on polymer particles intragranular rather than its surface.If the surface modification chemical is hydrophilic or can forms hydrogen bond (acid functional monomer of copolymerization is exactly this situation) with water, should believe then if the material of being discussed between the water of Aquo System and polymer beads surface at the interface, then polymer beads will be that thermodynamics is more stable.But because the character that polymer chain tangles, the polymer chain that contains the surface modification chemical may lack the essential flowability that moves to the interface between water and polymer beads surface.Therefore, be desirable to provide a kind of method that polymer beads includes the polymer chain flowability of mating surface modified chemical product that is increased in, control surface modified chemical product only are positioned at the position that needs, thereby increase the comprehensive effectiveness of the material effects of discussing.

Some different technology have been used to improve the flowability of polymer chain, but every kind of technology all has important disadvantages.For example, polymer beads can heat, and preferably is heated above the temperature of the second-order transition temperature of outer layer copolymer, and to increase the flowability of polymer chain, still, heating needs extra step and may make the polymer beads degraded.In addition, polymer beads can wear out time enough so that polymer chain moves to the most stable configuration of thermodynamics.This technology is unacceptable, because this to move required time compole long, and perhaps several months or even several years.The third scheme is to add organic solvent to make the outer deliquescing of polymer beads, thereby obtains the bigger flowability of polymer chain.This technology has stayed solvent in composition, it can cause safety, health and environmental problem, needs to remove.

EP 915,108 A disclose the method that a kind of preparation has the multistage emulsion polymers of the degree of swelling of improvement and dried density on expansion retentivity, comprise the following steps:

(a) under basic monomer-free polymeric condition, providing a kind of water miscible liquid, its by (i), (ii), (iii) constitute:

(i) multistage emulsion polymers comprises stratum nucleare polymkeric substance and shell polymkeric substance, and wherein, the stratum nucleare polymkeric substance contains as polymerized unit:

(1) in the stratum nucleare polymer weight, the wetting ability monoene of 5%～100% weight belong to unsaturated monomer and

(2) in the stratum nucleare polymer weight, at least a nonionic monoene of 0%～95% weight belongs to unsaturated monomer; And

Wherein, the nonionic monoene that contains as at least 50% weight that accounts for the shell polymer weight of polymerized unit of shell polymkeric substance belongs to unsaturated monomer; And

(ii) account for the monomer of at least 0.5% weight of multistage emulsion polymers weight; With

(iii) swelling agent; And

(b) monomer content reduces at least 50%.

EP 959, and 176A discloses a kind of method of controlling the position of the second shell polymkeric substance in the multistage polymer beads.Form the second shell polymkeric substance by following material: the gross weight in the second shell polymkeric substance is, at least a nonionic monoene of 93%～99.9% weight belong to unsaturated monomer and, gross weight in the second shell polymkeric substance is that the sour official of 0.1%～7% weight can belong to unsaturated monomer by monoene.The second-order transition temperature of this second shell polymkeric substance is-15 ℃～-50 ℃.

The applicant has had been found that a kind of preparation has the method for the polymer beads on chemical modification surface.By adopting this method, the applicant has prepared polymer beads, and wherein the surface modification chemical need not be introduced in that not need surface modification chemical or surface modification chemical be in the deleterious polymer beads part.

According to a first aspect of the invention, a kind of method of chemical modification of polymer particle surface is provided, comprise the following steps: that (1) provides a kind of water miscible liquid under basic monomer-free polymeric condition, it comprises: the multistage emulsion polymers that (a) comprises stratum nucleare polymkeric substance and shell polymkeric substance, wherein, the stratum nucleare polymkeric substance contains at least a nonionic monoene that the wetting ability monoene that accounts for stratum nucleare polymer weight 5%～100% weight as polymerized unit belongs to unsaturated monomer and account for stratum nucleare polymer weight 0%～95% weight and belongs to unsaturated monomer; And wherein, the nonionic monoene that contains as at least 50% weight of polymerized unit of shell polymkeric substance belongs to unsaturated monomer; (ii) account for the monomer of 0.5% weight of multistage emulsion polymers weight at least; (iii) at least a can with the chemically combined surface modification chemical of monomer; And (2) make monomer content reduce by 50% at least.

According to a second aspect of the invention, a kind of method of chemical modification of polymer particle surface is provided, comprising the following steps: provides a kind of water miscible liquid under (a) basic therein monomer-free polymeric condition, it comprises: the multistage emulsion polymers that (i) comprises stratum nucleare polymkeric substance and shell polymkeric substance, wherein, at least a nonionic monoene that accounts for stratum nucleare polymer weight 0.1%～100% weight that contains as polymerized unit of stratum nucleare polymkeric substance belongs to unsaturated monomer; And wherein, the shell polymkeric substance contains as polymerized unit: the nonionic monoene that (1) accounts at least 50% weight of shell polymer weight belongs to unsaturated monomer; (2) at least a surface modification monomer; (ii) account for the monomer of 0.5% weight of multistage emulsion polymers weight at least; (iii) neutralizing agent; And (b) monomer content is reduced by 50% at least.

According to a third aspect of the invention we, provide a kind of chemical modification of polymer particulate method, having comprised: (a) provide a kind of water miscible liquid under the basic therein monomer-free polymeric condition, it comprises: (i) emulsion polymer contains as polymerized unit:

(1) in the weight of described polymkeric substance, the wetting ability monoene of 5%～100% weight belongs to unsaturated monomer and (2) weight in described polymkeric substance, and at least a nonionic monoene of 0%～95% weight belongs to unsaturated monomer;

(ii) in the weight of described emulsion polymer, the monomer of at least 0.5% weight;

(iii) randomly, neutralizing agent; With

(iv) at least a can with the chemically combined surface modification chemical of described monomer; With

(b) described monomer content is reduced by 50% at least.

The layer of multistage polymkeric substance of the present invention comprises stratum nucleare polymkeric substance (" nuclear ") and shell polymkeric substance (" shell ")." nuclear " herein and " shell " not merely comprise the particle that spherical nucleus are wherein sealed by the shell of uniform thickness fully.But should be understood to also comprise other multistage polymer morphology, as multinuclear, nonspherical nucleus, shell in uneven thickness and the shell of fully nuclear not being sealed.In addition, nuclear and shell self can contain the structure more than one deck again.One or more middle layers can also be arranged.Preferably, multistage polymkeric substance comprises a nuclear, a middle layer and a shell.

The nuclear of multistage polymkeric substance of the present invention is emulsion polymer, it comprises as polymerized unit: at least a nonionic monoene that at least a wetting ability monoene that accounts for 5%～100% weight of this nuclear weight belongs to unsaturated monomer and accounts for 0%～95% weight of this stratum nucleare polymer weight belongs to unsaturated monomer.

The nuclear that at least a wetting ability monoene that contains at least 5 (weight) % that accounts for this nuclear polymer gross weight belongs to unsaturated monomer can make swelling capacity comparatively suitable usually.Also have some examples like this, wherein, because the hydrophobicity of some comonomer or their binding substances or combine, make this multipolymer to belong to unsaturated monomer and suitably prepare with accounting for the wetting ability monoene of this nuclear polymer gross weight less than 5 weight % with the hydrophobic/hydrophilic balance of special hydrophilic monomer.This nuclear preferably comprises as polymerized unit: account for 5%～100% of this nuclear gross weight, and more preferably 20%～60%, and the wetting ability monoene that most preferably is 30%～50% weight belongs to unsaturated monomer.This hydrophilic core polymkeric substance can prepare in independent stage of sequential polymerization or step, perhaps can be by the preparation of multistep order.

Multistage emulsion polymers of the present invention is imagined a kind of nuclear polymer, and wherein at least a wetting ability monoene belongs to unsaturated monomer separately or belong to unsaturated monomer with at least a nonionic monoene and carry out polymerization.This technology also imagined the non-polymeric compound that contains at least one carboxylic acid group that will be included among the term " the wetting ability monoene belongs to unsaturated monomer " (this compound before the polymerization of hydrophobicity shell polymeric, among or be absorbed afterwards enter in this nuclear polymer) belong to the surrogate of unsaturated monomer as the wetting ability monoene in the hydrophilic core polymkeric substance, see United States Patent (USP) 4 for details, 880,842.In addition, the present invention has also imagined the application that will be included in the potential hydrophilic core polymkeric substance among the term " the wetting ability monoene belongs to unsaturated monomer ", this nuclear polymer does not contain hydrophilic monoene and belongs to unsaturated monomer, but it is a kind of hydrophilic core polymkeric substance through the hydrolysis swellable, see United States Patent (USP) 5 for details, 157,084.

The suitable wetting ability monoene that is used to prepare this nuclear polymer belongs to unsaturated monomer and comprises: for example vinylformic acid, methacrylic acid, acryloxy propionic, methacryloxypropioniacid acid, methylene-succinic acid, equisetic acid, toxilic acid or maleic anhydride, fumaric acid, Ba Dousuan, maleic acid monomethyl ester, FUMARIC ACID TECH GRADE monomethyl ester, methylene-succinic acid monomethyl ester etc.Preferred vinylformic acid and methacrylic acid.

The suitable non-polymeric compound that contains at least one hydroxy-acid group comprises C ₆-C ₁₂Aliphatic series or one dollar aromatic carboxylic acid and di-carboxylic acid, as phenylformic acid, meta-toluic acid, Chlorodracylic acid, acetoxybenzoic acid, nonane diacid, sebacic acid, sad, hexahydrobenzoic acid, lauric acid and monobutyl phthalate etc.

The suitable nonionic monoene that is used to prepare the hydrophilic core polymkeric substance belongs to unsaturated monomer and comprises: vinylbenzene, alpha-methyl styrene, p-methylstyrene, t-butyl styrene, Vinyl toluene, ethene, vinyl acetate, vinylchlorid, vinylidene chloride, (methyl) vinyl cyanide, (methyl) acrylamide, (methyl) vinylformic acid (C ₁-C ₂₀) alkyl ester or (C ₃-C ₂₀) alkenyl ester (as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid hydroxypropyl ester, (methyl) benzyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid oil base ester, (methyl) vinylformic acid palm ester, (methyl) vinylformic acid stearyl etc.)." (methyl) acrylate " refers to acrylate or methacrylic ester herein.

No matter be to obtain from a single-step process or from a technology that comprises multistep, the median size of this nuclear not can be 50nm～1.0 μ m under the swollen condition, preferred 100nm～300nm.If this nuclear obtains by seed polymer, the median size of this seed polymer is preferably 30nm～200nm.

This nuclear also can randomly contain 0～20 weight % of this nuclear gross weight, and the polyenoid of preferred 0.1～3% weight belongs to unsaturated monomer, and wherein used amount generally roughly is directly proportional with the consumption that used wetting ability monoene belongs to unsaturated monomer; In other words, when the relative quantity of hydrophilic monomer increased, the content that polyenoid belongs to unsaturated monomer can increase.Perhaps, this nuclear polymer can contain the divinyl of 0.1～60% weight that accounts for the nuclear polymer gross weight.

Suitable polyenoid belongs to unsaturated monomer and comprises the acrylic acid alkylidene diol ester of two (methyl), for example ethylene glycol diacrylate, Ethylene glycol dimethacrylate, diacrylate 1,3-butanediol ester, diacrylate 1,4-butanediol ester, diacrylate propylene glycol ester and dimethacrylate triethyleneglycol ester; Dimethacrylate 1,3-glyceryl ester; 1,1,1-TriMethylolPropane(TMP) dimethacrylate; 1,1,1-trimethylolethane diacrylate; Trimethylammonium vinylformic acid pentaerythritol ester; 1,2,6-hexane triacrylate, pentamethyl-vinylformic acid sorbitol ester, methylene-bisacrylamide, the methylene-bis Methacrylamide, Vinylstyrene, the methacrylic acid vinyl ester, the butenoic acid vinyl acetate, vinyl acrylate, vinylacetylene, trivinylbenzene, triallylcyanurate, divinylacetylene, divinyl ethane, divinyl sulfuration thing, divinyl ether, divinylsulfone, diallyl cyanamide, the ethylene glycol bisthioglycolate vinyl ether, diallyl phthalate, the divinyl dimethylsilane, the glycerine trivinyl ether, hexanodioic acid divinyl ester; (methyl) vinylformic acid dicyclopentenyl ester; (methyl) vinylformic acid two cyclopentenes oxygen esters; The unsaturated ester of dibasic alcohol list dicyclopentenyl ether; α with unsaturated ethylene linkage end group, the allyl ester of β-unsaturated list and dicarboxylic acid (comprising: allyl methacrylate, vinylformic acid allyl ester, toxilic acid diallyl ester, fumaric acid diallyl ester, methylene-succinic acid diallyl ester etc.).

The multistage polymkeric substance of the present invention preferably contains a middle layer.This intermediate layer polymer when existing, partly or entirely seal nuclear, and itself is sealed partly or all seals by shell.This middle layer is carried out letex polymerization and is obtained in the presence of this nuclear.

This middle layer preferably contain as polymerized unit account for 0.3%～20% of this nuclear weight, more preferably at least a wetting ability monoene of 0.5%～10% weight belongs to unsaturated monomer.This middle layer preferably contain as polymerized unit account for 80%～99.7% of middle layer weight, more preferably at least a nonionic monoene of 90%～99.5% weight belongs to unsaturated monomer.This useful wetting ability monoene belongs to unsaturated monomer and belongs to unsaturated monomer with this nonionic monoene in this nuclear of preparation, also can be used for preparing this intermediate layer polymer.

The shell of the multistage polymkeric substance of the present invention is to account for this shell gross weight at least 50%, and is preferred 80%～100%, and more preferably at least a nonionic monoene of 90%～100% weight belongs to the product of unsaturated monomer letex polymerization.The nonionic monoene that is suitable for this nuclear belongs to unsaturated monomer and also is suitable for this shell.Optimization styrene.

This shell also can contain this shell weight 0%～20% that accounts for as polymerized unit, the monoene that one or more of preferred 0%～10% weight contain acidic functionality belongs to unsaturated monomer, comprising: vinylformic acid, methacrylic acid, acryloxy propionic, (methyl) acryloxy propionic, methylene-succinic acid, aconitic acid, toxilic acid, maleic anhydride, fumaric acid, Ba Dousuan, toxilic acid monomethyl ester, fumaric acid monomethyl ester, methylene-succinic acid monomethyl ester etc.Preferred vinylformic acid and methacrylic acid.

Obtain in the embodiment of hole emulsion polymer particle in hope, the alkaline neutraliser that the used monomer of shell polymeric and its relative proportion in shell should be able to make the volatile matter infiltration of water or gas phase or allow to this nuclear of swelling is fixed.In this case, the monomer mixture of the making shell monoene that preferably contains a kind of acidic functionality of 0.1%～10% weight that accounts for the shell polymeric gross weight belongs to unsaturated monomer.Preferably, the monoene of acidic functionality belongs to the ratio of unsaturated monomer in this shell polymeric and is no more than 1/3rd of its consumption in nuclear polymer.

The monoene that has acidic functionality in this shell polymeric belongs to the existence of unsaturated monomer, can play following several effect:

(1) stablize final multistage emulsion polymers,

(2) guarantee the permeable a kind of swelling agent of this shell, and

(3) layer that this shell and this multistage emulsion polymers are formerly formed is compatible.

Term used herein " the sequence letex polymerization " or " the sequence emulsion preparation " are meant a kind of in the presence of the dispersed polymeres particle of the emulsion polymer that formerly forms, in aqueous medium, polymkeric substance (comprising homopolymer and multipolymer) by the emulsion polymerization technique preparation, like this, formerly the size of the emulsion polymer of Xing Chenging increases to some extent by depositing emulsion polymeric product thereon, and the product of this letex polymerization is to continue to add one or more monomers to form in the medium of the dispersed particle that contains preformed emulsion polymer.

In the sequence letex polymerization of multistage emulsion polymers, term " seed " polymkeric substance is used in reference to a kind of dispersion liquid of aqueous emulsion polymers, it can be the initial dispersion liquid that forms, that is: the product of a step letex polymerization perhaps can be the emulsion polymer dispersion liquid that the end in other any follow-up phase except the terminal stage of sequential polymerization obtains.Therefore, hydrophilic nuclear polymer (attempting to be sealed) by one or more follow-up letex polymerization stages at this, himself just can be called the seed polymer of next stage.

The inventive method comprises: nuclear, middle layer, shell, or their any combination can make by an independent sequential polymerization stage or a step perhaps can make by successively many steps after this polymerization.In the fs of the letex polymerization of technology of the present invention can be the short grained seed polymer of dispersed polymeres that preparation contains water insoluble letex polymerization medium.This seed polymer can contain or not contain any hydrophilic monomer composition, but the nuclear that forms thereon with or without the hydrophilic core polymkeric substance of non-ionic co-monomers is provided.

The emulsion polymer of third aspect present invention contains as the wetting ability of polymerized unit and nonionic monoene and belongs to unsaturated monomer, and suitable monomers comprises the monomer that exemplifies for the nuclear polymer of multistage emulsion polymers on those this.

In this aqueous emulsion polymerization, used a kind of water-soluble radical initiator.Suitable water-soluble radical initiator comprises: hydrogen peroxide; Tert-butyl peroxide; Tert-butyl hydroperoxide; T-amyl hydroperoxide; The persulfuric acid an alkali metal salt is as Sodium Persulfate, Potassium Persulphate and persulfuric acid lithium; Ammonium persulphate; And the mixture of these initiators and reductive agent.Reductive agent comprises: sulphite, as: alkali-metal metabisulphite, hydrosulphite and hyposulfite; Formaldehyde sodium sulfoxylate and reducing sugar such as ascorbic acid and saccharosonic acid.The amount of this initiator preferably accounts for 0.01%～3% weight of total monomer weight, and the amount of reductive agent preferably accounts for 0.01%～3% weight of total monomer weight in redox system.Temperature can be in 10 ℃～100 ℃ scope.When adopting the persulphate system, temperature is preferably in 60 ℃～90 ℃ scope.In redox system, temperature preferably in 30 ℃～70 ℃ scope, preferably is lower than 60 ℃, more preferably 30 ℃～45 ℃.The type of initiator and amount can be identical or different in each step at multistage polymeric.

Can be separately or use one or more nonionics or anionic emulsifier or tensio-active agent together.The example of suitable nonionic emulsifying agent comprises: many (the 39)-ethoxy ethanols of uncle's Octylphenoxy ethyl, dodecyloxy many (10) ethoxy ethanol, Nonylphenoxy ethyl-many (40) ethoxy ethanol, Macrogol 2000-monoleate, ethoxylated castor oil, fluorinated alkyl esters and alcoxylates, polyoxyethylene (20) Arlacel-20, single coconut sucrose ester, two (2-butyl) phenoxy group many (20) ethoxy ethanol, many butylacrylic acid of Natvosol ester graft copolymer, the segmented copolymer of poly-(oxyethane)/poly-(butyl acrylate), the segmented copolymer of propylene oxide and oxyethane, with 2 of 30 moles oxyethane ethoxylations, 4,7,9-tetramethyl--5-decine-4, the 7-glycol, N-polyoxyethylene (20) laurylamide, N-lauryl-N-polyoxyethylene (3) amine and poly-(10) ethylene glycol dodecyl thioether.The example of suitable anionic emulsifier comprises Sodium Lauryl Sulphate BP/USP, Sodium dodecylbenzene sulfonate, potassium stearate, dioctyl sodium sulphosuccinate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, the Nonylphenoxy ethyl gathers (1) ethoxyethyl group ammonium sulfate, Sodium styrene sulfonate, dodecyl allyl group sodium sulfosuccinate, linseed oil fatty acid, the sodium salt of ethoxylated nonylphenol phosphoric acid ester or ammonium salt, hot oxygen alcohol-3-sodium sulfonate, coco group Sha Kangxin sodium (sodium cocoyl sarcocinate), 1-alkoxyl group-2-hydroxypropyl azochlorosulfonate acid sodium, alpha-olefin (C ₁₄-C ₁₆) sulfuric ester, N-(1,2-dicarboxyl ethyl)-N-18 sulfosuccinamic acids four sodium, N-octadecyl sulfosuccinamic acid disodium, the alkyl amido polyethoxye disodium sulfosuccinate of sodium sulfonate, hydroxyl alkanol, the ethoxylated nonylphenol Carbenoxolone Sodium and poly-(39) the ethoxyethyl vitriolic sodium salt of uncle's octyl group benzene oxygen oxyethyl group of sulfo-succinic acid.The common consumption of these one or more tensio-active agents accounts for 0～3% weight of this grade polymer weight.During adding any monomer feed or its a kind of mixture, can before adding any monomer feed, add tensio-active agent earlier.In being used to form some monomer/emulsifier system of shell, do not damaging this polymkeric substance under the sedimentary prerequisite on the nuclear particle in preceding formation, account for the emulsifying agent of this shell polymeric gross weight 0.05%～2.0% weight by adding, can reduce or prevent in reaction medium, to form the tendency of gel or floss.

When using persulfate initiator, the addition of emulsifying agent can be for 0 to 3% weight that accounts for this nuclear polymer gross weight.When keeping the low levels emulsifying agent, by carrying out letex polymerization, each step subsequently that forms polymkeric substance with the polymer precipitation of up-to-date formation on back or the already present dispersive polymer particle that forms previous stage.As universal law, the amount of this emulsifying agent should keep below the corresponding micelle-forming concentration of a certain monomers system, yet, though preferably this boundary and its have prepared the product of single form, but found that in some system the micelle-forming concentration of this emulsifying agent can have some to surpass and not have to form the dispersion micelle or the particle of harmful or excessive number.It is in order in the polymeric different steps micellar number to be controlled so that the polymer deposition that forms subsequently in each step goes on foot on the dispersive micella or particle that forms before occurring in that emulsifying agent keeps lower concentration.

The weight-average molecular weight (use gel permeation chromatography) of the polymkeric substance that forms in given stage can be from 100,000 (or, if used chain-transfer agent to hang down) arrive millions of.When in when nuclear preparation, use a kind of polyenoid mentioned before this that accounts for monomer weight 0.1%～20% weight to belong to unsaturated monomer, whether no matter taken place crosslinkedly, molecular weight all increases.When handling multistage polymkeric substance, use polyenoid to belong to unsaturated monomer and reduced this nuclear polymer dissolved tendency with the swelling agent of this nuclear.If wish the low side of preparation molecular weight in described scope, as molecular weight is 20,000 to 500, during 000 nuclear, usually the most practical method is to use a kind of chain-transfer agent without polyenoid belongs to unsaturated monomer, for example: 0.05%～2% weight of this strata compound weight or higher, for example, alkyl sulfhydryl or sulfydryl chain acid alkyl ester.

Nuclear is generally 1: 0.5 with the weight ratio in middle layer (if any)～and 1: 10, preferred 1: 1～1: 7.Nuclear is generally 1: 5 with the weight ratio of shell～and 1: 20, preferred 1: 8～1: 15.

No matter this shell polymeric forms in single step or in multistep, the amount of the polymkeric substance of formation of deposits shell polymeric is general, for example, make (promptly pH is being brought up at least 6 any neutralization reaction before) under the non-swelling condition, the external diameter scope of multistage polymer particle is at 70nm～4.5 μ m, preferred 100nm～3.5 μ m, more preferably 200nm～2.0 μ m.Whole when encapsulated when the hydrophilic core polymkeric substance, under the analysis condition of about 1 hour and room temperature, it is carried out titration without alkali metal base.The degree of sealing can be used in this shell polymeric process, takes sample away, and carries out titration with sodium hydroxide and measure.

This multistage emulsion polymers can prepare by the sequence letex polymerization, and this polymerization process comprises adding the monomer that forms shell as mentioned above.Add when finishing at the monomer that forms shell, or when finishing, content comprises in the reactor: multistage polymkeric substance, water and unreacted monomer.Under the condition of letex polymerization, also have significant free-radical contents, or the free radical flow, it can guarantee that polymerization process proceeds.Even without other interpolation monomer or initiator, in system, still there is the free radical of suitable content.When not having the free radical of suitable content, in other words very low or when approaching 0 when this free radical flow, can a large amount of polymerizations not take place just.

We find that free-radical contents can influence obtainable degree of swelling.In the former known technology, typically obtain the swollen method and be:, obtain swelling by adding suitable swelling agent adding after monomeric latter stage that forms shell or the monomeric adding that is forming shell finish.It is believed that and exist unreacted monomer to help swelling agent is transported to nuclear.Yet in the former known technology, swelling agent is to add this system when also having the free radical of a great deal of in this system.Therefore under those conditions, still a large amount of polyreactions can take place.

We find by the water miscible liquid of multistage emulsion polymers, monomer and neutralizing agent, can strengthen the degree of swelling of this multistage emulsion polymers not having under the condition of a large amount of monomer polymerizations.

Can provide a lot of means to make monomer that a large amount of polymerizations not take place, comprise: add one or more stoppers, add one or more reductive agents, wait for that the sufficiently long time no longer includes the free radical of significant amounts, the content in the cooling reactor reactivity with the restraint of liberty base until the effectiveness termination of free radical, and with they bonded methods.Preferable methods relates to and adds one or more stoppers, for example: N, the N-diethyl hydroxylamine, N nitrosodiphenyl amine, 2, the 4-dinitrophenylhydrazine, Ursol D, thiodiphenylamine, 2,6-dimethyl-octa-2,4, the 6-triolefin, triethyl-phosphite, the 4-nitrosophenol, the 2-nitrophenols, p-aminophenol, 4-hydroxyl-TEMPO (4-hydroxyl-2,2,6,6-four phenylpiperidines oxygen bases, free radical), quinhydrones, to the methoxyl group quinhydrones, the tertiary butyl is to quinhydrones, 2, the 5-di-t-butyl is to quinhydrones, 1, the 4-naphthalenediol, the 4-tert-butyl catechol, copper sulfate, cupric nitrate, cresols and phenol.When using, add the stopper of significant quantity or reductive agent to stop any polymerization basically, add-on is 25/1000000ths～5,000 part (" ppm ") of polymer solids weight usually, and is preferred 50～3,500ppm.Preferably, when the temperature of multistage polymkeric substance is in or is lower than shell and carries out the polymeric temperature, add stopper or reductive agent, most preferably be lower than the shell polymerization temperature and be no more than 10 ℃.

After hypothesis did not have a large amount of monomer polymerization generations, the monomer of existence can be:

(i) one or more are used for preparing this monomer of arbitrary layer multistage or single polymer layer;

(ii) one or more monomers except those are used for preparing the monomer of arbitrary layer of multistage or single polymer layer; Or

(iii) their combination.

The monomer that exist preferred this moment is one or more monomers that are used to prepare shell.Unreacted monomer when these monomers can be this multistage emulsion polymers of preparation also can be to add separately, or their array configuration.Preferred this monomer is a non-ionic monomer.Preferred use non-ionic monomer can be neutralized the agent neutralization because have the monomer of acidic functionality, and these neutral monomers is difficult to remove by polymerization.Preferably hypothesis do not have a large amount of monomer polymerization take place after the monomeric content of existence be 1～20 times of standard monomer content between polymerization period.

The surface modification chemical that is used for technology of the present invention be any can with the chemically combined chemical of ethylenically unsaturated monomer, its content for the step (a) of the method for claim 1～3 of the present invention (ii) at least 0.5% weight of emulsion polymer weight.Kinds of surface modified chemical product can be used for the inventive method, comprise monomer, oligopolymer, Natvosol or other Mierocrystalline cellulose of terminal unsaturation, polyvinyl alcohol, poly-(N-vinyl pyrrolidone) and polyacrylamide with the unsaturated position of at least one olefinic.

The amount that is used for the surface modification chemical of the inventive method depends primarily on the final quantity that hope is present in the compound of surface of emulsion polymer particles.Preferably with the dry weight basis of polymer beads, the add-on of surface modification chemical can be 0.1%～10% weight, more preferably 0.2%～7.5% weight.

Preferred one or more neutralizing agents that use.Suitable neutralizing agent comprise those multistage emulsion polymers and monomeric in the presence of, can permeate shell and swelling nuclear neutralizing agent.Neutralizing agent can be water-based or gaseous state, volatile or fixed alkali or its array configuration.

Suitable neutralizing agent comprises volatilization alkali such as ammonia, ammonium hydroxide and volatility lower aliphatic amine such as morpholine, Trimethylamine 99 and triethylamine etc.; Fixing or permanent alkali such as potassium hydroxide, lithium hydroxide, zinc ammonium complex, cuprammonium complex, silver-colored ammonium complex compound, strontium hydroxide, hydrated barta etc.Can add solvent such as ethanol, hexanol, octanol, TEXANOL solvent and those at United States Patent (USP) 4,594, the solvent described in 363 is to help the infiltration of fixing or permanent alkali.Preferred ammonia and ammonium hydroxide.

When attempting to make the degree of swelling maximization, preferably after were it not for monomeric a large amount of polymerization generation, add one or more neutralizing agents.The amount of neutralizing agent can less than, be equal to or greater than fully the required amount of neutralization nuclear.The amount of neutralizing agent is preferably 75～300% of functional group's equivalent value of accounting for the nuclear that can be neutralized, and more preferably 90%～250%.Also preferably when multistage emulsion polymers is in the temperature of rising, in multistage emulsion polymers, add one or more neutralizing agents, preferably in 10 ℃ of scopes of shell polymerization temperature, add.When monomer existed and do not have a large amount of polymerizations to take place, under the temperature condition that raises, swelling was generally very effective.Under these conditions, count from adding one or more swelling agents, swelling in 30 minutes, preferably in 20 minutes, was most preferably finished in 10 minutes usually.

When this nuclear is handled with a kind of alkaline swelling agent, nuclear polymer meeting swelling in this multistage emulsion polymers, the hydrophilic functional group of permeable this shell of this alkalescence swelling agent this nuclear so that small part neutralizes, the pH value preferably is at least about 6, more preferably pH is at least about 10, thereby has caused the swelling of this hydrophilic core polymkeric substance.The outer edge part that the swelling of nuclear or expansion can cause examining is fused in the hole of preglabellar field of shell, and part enlarges or expanded this shell and whole particle generally.

When with swelling multistage emulsion polymers when dry, remove from the central zone of swollen multistage emulsion polymers and to anhydrate and/or neutralizing agent, nuclear is tending towards shrinking, and forms hole, the degree of hole depends on this shell to recovering drag of size before its.Shell drops to minimum to the drag of recovering original size to the dried tap density with the swollen multistage emulsion polymers and plays a crucial role.The expansion of nuclear causes shell also to expand.It is original when big or small when the size of shell returns to, and doing tap density increases.Therefore wish that the big or small recovery extent of this shell drops to minimum, thus the dried tap density of maximizing swollen multistage emulsion polymers.

This can finish by reducing monomeric content.It is believed that monomeric existence makes multistage polymkeric substance be easy to swelling, or this is by plasticizing shell, auxiliary through the transmission of shell to inside, perhaps passes through their array configuration and realizes.Yet when doing tap density when the degree of swelling maximization of attempting to make the swollen multistage emulsion polymers and minimizing, monomeric existence may be deleterious.Therefore under the situation of monomer and swelling agent both existence, after the multistage emulsion polymers swelling, wish monomeric content is reduced to less than 10 of polymer solids, 000ppm, preferably less than 5,000ppm.This can finish by any suitable method, and preferably the mode by monomer polymerization reduces monomeric content.It can be by any suitable manner, as finishing by adding one or more those initiators as previously described.Preferably in 20 minutes after adding one or more swelling agents, more preferably in 10 minutes, begin to reduce monomeric content.

Now, in the following example, describe embodiments more of the present invention in detail.

Abbreviation

The MMA=methyl methacrylate

The MAA=methacrylic acid

AA=vinylformic acid

The EA=ethyl propenoate

The BA=butyl acrylate

STY=vinylbenzene

The SPS=Sodium Persulfate

The NaDDBS=Sodium dodecylbenzene sulfonate

The IAA=saccharosonic acid

DI water=deionized water

Experimental technique

The mensuration of polymer dry density

Dry density according to following method mensuration polymkeric substance comprises the latex sample of dilution centrifugal.In the 50ml centrifuge tube, add the 6.3g polymer solids.DI water is joined in the centrifuge tube so that the gross weight of adding material is 35g.This is corresponding to 18% of polymer solids weight.With 18,000 rotating speeds/minute the rotation 120 minutes.Outwell supernatant liquor and weigh.Measure dry density by following equation then.

d _dry＝V％ _p×d _p ${V\%}_p=1-{V\%}_{H_{2}O}$ ${V\%}_{H_{2}O}=\frac{V_{H_{2}O}}{V_{H_{2}O}+V_p}=\frac{(V_T-S_{H_{2}O})\×C_{\mathrm{Pac}}-V_p}{(V_T-S_{H_{2}O})\×C_{\mathrm{Pac}}}$ $V_{H_{2}O}=(V_T-S_{H_{2}O})\×C_{\mathrm{Pac}}-V_p$ $V_{H_{2}O}+V_p=(\mathrm{VT}-S_{H_{2}O}){\×C}_{\mathrm{Pac}}$

Wherein:

d _Do=polymer dry density

d _p=density polymer=1.084g/mL

d _H2O=water-mass density=1.000g/mL

V% _pThe volume percent of=polymkeric substance in particle

V% _H2OThe volume percent of water in the=particle

W _PWeight=the 35.00g of polymkeric substance * 18%=6.30g in the=pipe

V _H2OThe volume of water in the=particle

I _H2O=interstitial water volume

S _H2OWeight/the d of the volume=supernatant liquor of=supernatant liquor _H2OThe weight of=supernatant liquor

V _P=polymer volume=6.30g ÷ 1.084g/mL=5.81mL

V _TCumulative volume in the=pipe=(W _T-W _P)/d _H2O+ V _P=28.70mL+5.81mL=34.5

C _PacPile up constant, with the not swelling latex calculating of similar particle diameter

Use C then _PacMean value

Latex particle size C _Pac

Embodiment 3 417nm 0.622

Embodiment 4 420nm 0.624

Comparative example B 426nm 0.633

Embodiment 8 444nm 0.616

Comparative example D 425nm 0.631

On average-0.625 therefore: $d_{\mathrm{dry}}=\frac{V_p\×d_p}{(V_T-S_{H_{2}O})\×C_{\mathrm{Pac}}}=\frac{5.81\×1.084}{(34.51-S_{H_{2}O})\×0.625}=\frac{10.08}{34.51-S_{H_{2}O}}g/\mathrm{mL}$

Nuclear polymer A. prepares nuclear polymer

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1700g), and be heated to 85 ℃.Monomer emulsion (ME) prepares by mixing 720g DI water, 5.2g DISPONIL FES-993 tensio-active agent (DISPONIL is the trade mark of Henkel Corp.), 10.0g MAA and 780g MMA.From ME, take out 164g and be put in one side.In remaining ME, add 54.6gDISPONIL FES-993,260.0g MMA, 250.0g MAA and 100.0g DI water.When the water in the reactor is 85 ℃, add following material successively: solution, the ME that from initial monomer emulsion take out and 20.0g washing water, 5.5g SPS the solution in 40.0g DI water of 1.5g DISPONIL  FES-993 in 150.0g DI water.Contents stirred in the reactor 15 minutes.At 85 ℃, remaining ME is joined in the reactor through two hours.After adding monomer, with 30.0g DI water washing ME container.Then dispersion liquid was placed 20 minutes at 85 ℃ again, be cooled to 25 ℃, and remove by filter any condensation product.The pH of filtering dispersion liquid is 2.4, and solid content is 31.7%, and median size is 150nm.

Nuclear polymer B. prepares nuclear polymer

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1850g), and be heated to 85 ℃.Monomer emulsion (ME) prepares by mixing 720g DI water, 5.2g DISPONIL FES-993 tensio-active agent, 10.0g MAA and 845g MMA.From this ME, take out 164g ME and be put in one side.In remaining ME, add 54.6g DISPONIL FES-993 tensio-active agent, 445.0g MMA and 50.0g DI water.When the water in the reactor is 85 ℃, add following material successively: solution, the ME that from initial monomer emulsion take out and 20.0gDI water, 5.5g SPS the solution in 40.0g DI water of 0.5g DISPONIL FES-993 tensio-active agent in 70.0g DI water.Contents stirred in the reactor 15 minutes.At 85 ℃, remaining ME is joined in the reactor through two hours.After adding monomer, with 30.0g DI water washing ME container.Then dispersion liquid was placed 20 minutes at 85 ℃ again, be cooled to 25 ℃, and remove by filter any condensation product.The pH of filtering dispersion liquid is 2.3, and solid content is 31.6%, and median size is 182nm.

Nuclear polymer C. prepares nuclear polymer

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.In this reactor, add DI water (1675g), and under nitrogen atmosphere, be heated to 89 ℃.Monomer emulsion (ME) prepares by mixing 720g DI water, 4.08g DISPONIL FES-993 tensio-active agent (DISPONIL is the trade mark of Henkel), 10.8g MAA and 804g MMA.From this ME, take out 151.5g ME and be put in one side.In remaining ME, add 20.86gDISPONIL FES-993 and 526.0g MMA.When the water in the reactor is 89 ℃, add following material successively: solution, the ME that from initial monomer emulsion take out and 25.0g washing water, 5.7g SPS the solution in 30.0g DI water of 0.54g DISPONIL FES-993 in 150.0g DI water.Content in the reactor stirred 20 minutes at 80 ℃.At 80 ℃, remaining ME is joined in the reactor through two hours.After adding monomer, with 30.0g DI water washing ME container.Then dispersion liquid was placed 20 minutes at 80 ℃ again, be cooled to 25 ℃, and remove by filter any condensation product.The pH of filtering dispersion liquid is 2.3, and solid content is 31.7%, and median size is 380nm.

Embodiment 1. preparations have the emulsion polymer particle on chemical modification surface.Except retaining (held-out) part, MAA is (ME II) in whole shell.After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1400g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (in water 23%), 50g STY, 44g MMA and 6gMAA, and it is added in reactor through 40 minutes at 78 ℃.Add ME I, the 40g DI water washing of this container.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 10gNaDDBS (23%) and 679g STY.From this ME II, take out 133g and be put in one side.In remaining ME II, add MAA (21g) then.Through 60 minutes ME II joined in the reactor and with the speed common 1.0g SPS of adding solution in 60g DI water in reactor of 1g/min.The temperature of reactor rises to 92 ℃.After adding ME II and SPS, the 40g DI water washing of ME II container.Make reaction mixture be cooled to 85 ℃.Add 20g 0.1% ferric sulfate and 2g 1% according to ground alkene (versene), and placing response content 15 minutes.The mixture that adds 5g 5% 4-hydroxyl TEMPO and 10g DI water adds ME II (133g) and the 40g DI water of retaining part then.Add subsequently ammonium hydroxide (28%, 40.3g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 28.9%, and pH is 10.2, and particle diameter is 416nm.Press US4,427,836 is described, and final latex is incorporated in the film to measure KubelkaMunk scattering coefficient (S/mil).The S/mil of the film that obtains is 0.45.Measuring dry density with the method for experimental technique part is 0.703g/mL.Acidometric titration shows that whey does not contain any acid.The titration (with AMBERLITE IRN-77 ion exchange resin (AMBERLITE be the trade mark of Rohm and Hass Company) handle back) of deionization latex in water shows that 24% shell acid is titratable, and is positioned on the latex surface.

Embodiment 2. preparations have the emulsion polymer particle on chemical modification surface.MAA is (ME II is except retaining part) in the second half shells.After the shell polymerization, neutralize.

Repeat embodiment 1, except after removing the ME II that 133g retains, MAA being joined among the second half remaining ME II.That is, remaining ME II is divided into two equal parts.MAA is joined second section.The ME II that does not have the MAA part when adding beginning then adds the ME II that has the MAA part subsequently.Joining day keeps identical.The solids content of final latex is 29.3%, and pH is 10.2, and particle diameter is 443nm, and S/mil is 0.29.The dry density of measuring is 0.687.Acidometric titration represents that whey does not contain any acid.The titration (with AMBERLITE  IRN-77 ion exchange resin treatment after) of deionization latex in water shows that 53% shell acid is titratable and is positioned on the latex surface.

Comparative Examples A. the preparation emulsion polymer particle.MAA is (ME II) in whole shell.After half takes place in the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1400g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY, 44g MMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, container 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 10g NaDDBS (23%), 679g STY and 21g MAA.Through 65 minutes ME II is joined in the reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.9g/min.Make the temperature of reactor rise to 92 ℃.When adding half ME II, in reaction mixture, add ammonium hydroxide (28%, 40.3g).After adding ME II and SPS, with 80g DI water washing ME II container.Make reaction mixture be cooled to 85 ℃.Add 20g 0.1% ferric sulfate and 2g 1% according to the mixture of ground alkene, add 0.8gSPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water again.After adding the solution of 0.7g IAA in 20g DI water, reaction mixture kept 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 28.5%, and pH is 9.6, and particle diameter is 422nm, and S/mil is 0.39.The mensuration dry density is 0.832g/mL.Acidometric titration shows that whey contains 41% ME II acid.Similarly, use the acidometric titration of the whey of AMBERLITE IRN-77 ion exchange resin deionization, show that it contains 39% ME II acid.The titration of deionization shows that 57% shell acid is titratable in the water, shows that 18% shell acid is positioned at the latex surface.

The methacrylic acid of table 1. embodiment 1-2 and Comparative Examples A distributes

The acid of emulsion polymer % copolymerization on particle surface

Embodiment 1 24%

Embodiment 2 53%

Comparative Examples A 18%

The emulsion polymer particle that the method for embodiment of the invention 1-2 provides comparison to have higher surface acid than embodiment A method.

Embodiment 3. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, MAA is (ME) in whole shell.After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1500g), and be heated to 85 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then (44.7% solid is 96nm) with 20g DI water to add 22.3g acrylate copolymer dispersion liquid.Monomer emulsion (ME) prepares by mixing 250g DI water, 12g NaDDBS (23%) and 970gSTY.From this ME, take out 184g and place one side.In remaining ME, add MAA (30g) then.Added ME through 90 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.After adding ME and SPS, the 40g DI water washing of ME container.Add 20g0.1% ferric sulfate and 2g 1% mixture, and reaction content was placed 15 minutes at 92 ℃ according to ground alkene.The mixture that adds 5g 5% 4-hydroxyl TEMPO and 10g DI water adds ME (184g) and the 40g DI water of retaining part then.During adding, reaction mixture is cooled to 85 ℃.Add then ammonium hydroxide (28%, 31.8g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 32.6%, and pH is 9.7, and particle diameter is 417nm.Acidometric titration shows that whey does not contain the polynary or monoprotic acid of any neutral.The titration (with AMBERLITE IRN-77 ion exchange resin treatment after) of deionization latex in water shows that 16% shell acid is titratable and on the latex surface.

Embodiment 4. preparations have the emulsion polymer particle on chemical modification surface.MAA is (ME is except the part of taking out) in the second half shells.After the shell polymerization, neutralize.

Repeat embodiment 3, except after the ME that remove to take out, MMA being joined among the second half remaining ME.That is, take out 184g ME and place one side, remaining ME II is divided into two equal parts.MAA (30g) is joined second section.Add the ME II that does not have the MAA part during beginning, add the ME II that has the MAA part subsequently.It is identical that the adding speed of ME and SPS keeps.The solids content of final latex is 32.3%, and pH is 9.9, and particle diameter is 420nm.The whey of representing acidometric titration does not contain the polynary or monoprotic acid of any neutral.The titration (with AMBERLITE IRN-77 ion exchange resin treatment after) of deionization latex in water shows that 28% shell acid is titratable and is positioned on the latex surface.

Comparative example B. prepares emulsion polymer particle.MAA is in whole shell.After carrying out half, the shell polymerization neutralizes.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.In this reactor, add DI water (1500g), and under nitrogen atmosphere, be heated to 85 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then (44.7% solid is 96nm) with 20g DI water to add 22.3g acrylate copolymer dispersion liquid.Monomer emulsion (ME) prepares by mixing 250g DI water, 12g NaDDBS (23%), 970g STY and 30g MAA.Added ME through 90 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.Add ME after half, in reaction mixture, add ammonium hydroxide (28%, 31.8g).After adding ME and SPS, the 80g DI water washing of ME container.Reaction mixture is cooled to 85 ℃, adds 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 32.3%, and pH is 9.7, and particle diameter is 426nm.Acidometric titration shows that whey contains 57% shell acid.The titration (with AMBERLITEIRN-77 ion exchange resin treatment after) of deionization latex in water shows that 55% shell acid is titratable, and all titratable acid whey mutually in.

The methacrylic acid of table 2. embodiment 3-4 and comparative example B distributes

The co-polymeric acids of emulsion polymer % on particle surface

Embodiment 3 16%

Embodiment 4 28%

Comparative example B 0%

The emulsion polymer particle that the method for embodiment of the invention 3-4 provides comparison to have higher surface acid than Embodiment B method.

Embodiment 5. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, vinylformic acid is (ME II) in whole shell.After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1400g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY, 44gMMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, with this container of 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 10g NaDDBS (23%) and 686g STY.From this ME II, take out 133g and place one side.Then AA (14g) is joined among the remaining ME II.Added MEII through 60 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 1g/min.The temperature of reactor rises to 92 ℃.After adding ME II and SPS, the 40g DI water washing of ME II container.Make reaction mixture be cooled to 85 ℃.Add 20g 0.1% ferric sulfate and 2g 1% mixture, and reaction content was placed 15 minutes according to ground alkene.The mixture that adds 5g 5%4-hydroxyl TEMPO and 10g DI water adds ME II (133g) and the 40g DI water of retaining part then.Add subsequently ammonium hydroxide (28%, 32.0g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 28.8%, and pH is 9.9, and particle diameter is 424nm, and S/mil is 0.40.The mensuration dry density is 0.719g/mL.Acidometric titration shows that whey contains 28% shell acid.The titration (with AMBERLITE IRN-77 ion exchange resin treatment after) of deionization latex in water shows that 50% shell acid is titratable, shows that 36% acid is positioned at particle surface.

Embodiment 6. preparations have the emulsion polymer particle on chemical modification surface.Vinylformic acid is (ME II is except retaining part) in the second half shells.After the shell polymerization, neutralize.

Repeat embodiment 5, except after the ME II that remove to retain, AA being joined among the second half remaining ME II.That is, take out behind the 133g ME II and placement one side, remaining ME II is separated into two equal parts.AA is joined second section.Adding when ME II begins is not have the AA part, then has AA subsequently.Add speed and keep identical.The solids content of final latex is 28.7%, and pH is 10.2, and particle diameter is 398nm, and S/mil is 0.46.The mensuration dry density is 0.687g/mL.The whey of representing acidometric titration contains 37% shell acid.The titration (with AMBERLITE IRN-77 ion exchange resin treatment after) of deionization latex in water shows that 62% shell acid is titratable, shows that 45% acid is positioned on the particle surface.

Comparative example C. prepares emulsion polymer particle.Propylene is (ME II) in whole shell.After carrying out half, the shell polymerization neutralizes.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1400g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY and 44g MMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, container 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 10g NaDDBS (23%) and 686g STY and 14g AA.Added ME II through 65 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.9g/min.The temperature of reactor rises to 92 ℃.When adding half ME II, in reaction mixture, add ammonium hydroxide (28%, 37.3g).After adding ME II and SPS, the 80g DI water washing of ME II container.Reaction mixture is cooled to 85 ℃, adds 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water then.After adding the solution of 0.7g IAA in 20g DI water, reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 28.8%, and pH is 10.0, and particle diameter is 494nm, and S/mil is 0.40.The mensuration dry density is 0.808g/mL.The whey of representing acidometric titration contains 63% ME II acid.The titration (with AMBERLITEIRN-77 ion exchange resin treatment after) of deionization latex in water shows that 76% shell acid is titratable, shows that 28% acid is positioned on the particle surface.

The vinylformic acid of table 3. embodiment 5-6 and comparative example C distributes

But the acid of emulsion polymer % copolymerization on particle surface

Embodiment 5 36%

Embodiment 6 45%

Comparative example C 28%

The emulsion polymer particle that the method for embodiment of the invention 5-6 provides comparison to have higher surface acid than Embodiment C method.

Embodiment 7. preparations have the emulsion polymer on chemical modification surface.Vinylformic acid is positioned at shell (ME III).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1400g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY, 44gMMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, with this container of 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 150g DI water, 8g NaDDBS (23%) and 600g STY, takes out 128g and place one side from this ME II.Added ME II through 60 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.76g/min.The temperature of reactor rises to 92 ℃.After adding ME II, the 40g DI water washing of ME II container.Make reaction mixture be cooled to 85 ℃.The 3rd monomer emulsion (ME III) prepares from 50g DI water, 3g NaDDBS (23%), 95g MMA and 5g AA, adds this ME III through 20 minutes in the clockwise reaction mixture.After adding ME III and SPS, with 40g DI water washing container ME III.Add 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene, reaction content was placed 15 minutes.The mixture that adds 5g 5% 4-hydroxyl TEMPO and 10g DI water adds ME II (133g) and the 40g DI water of retaining part then.Add then ammonium hydroxide (28%, 26.1g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45gDI water, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 28.4%, and pH is 9.8, and particle diameter is 424nm, and S/mil is 0.27.The mensuration dry density is 0.684g/mL.Acidometric titration shows that whey contains 20% shell acid.The titration (with AMBERLITE IRN-77 ion exchange resin treatment after) of deionization latex in water shows that total titratable acid is 108% shell acid.

Embodiment 8. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, vinylformic acid is positioned at whole shell (ME).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1500g), and be heated to 85 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then (44.7% solid is 96nm) with 20g DI water to add 22.3g acrylate copolymer dispersion liquid.Monomer emulsion (ME) prepares by mixing 250g DI water, 12g NaDDBS (23%) and 980gSTY.From this ME, take out 184g and place one side.In the ME of remnants, add AA (20g) then.Added this ME through 90 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.Temperature rises to 92 ℃.After adding ME and SPS, with this MI container of 40g DI water washing.Add 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene, reaction content was placed 15 minutes at 92 ℃.The mixture that adds 5g 5%4-hydroxyl TEMPO and 10g DI water adds ME (184g) and the 40g DI water of retaining part then.During adding, reaction mixture is cooled to 85 ℃.Add then ammonium hydroxide (28%, 25.3g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 32.3%, and pH is 10.0, and particle diameter is 444nm.Acidometric titration shows that whey contains 18% shell acid.The titration (with AMBERLITE IRN-77 ion exchange resin treatment after) of deionization latex in water shows that 40% shell acid is titratable, shows that 22% AA that adds is positioned at the latex surface.

Comparative example D. prepares emulsion polymer particle.Propylene is positioned at whole shell.After carrying out half, the shell polymerization neutralizes.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1500g), and be heated to 85 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then (44.7% solid is 96nm) with 20g DI water to add 22.3g acrylate copolymer dispersion liquid.Monomer emulsion (ME) prepares by mixing 250g DI water, 12g NaDDBS (23%), 900gSTY and 20g AA.Added this ME through 90 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.Temperature rises to 92 ℃.When adding half ME, in reaction mixture, add ammonium hydroxide (28%, 31.8g).In the time of after adding ME and SPS, with 80g DI water washing ME container.Reaction mixture is cooled to 85 ℃, and adds 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water then, add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 33.1%, and pH is 10.0, and particle diameter is 425nm.Acidometric titration shows that whey contains 72% shell acid.Titration at the water-borne glue breast shows that 74% shell acid is titratable, and indicating only has a spot of vinylformic acid to be positioned at the latex surface.

The vinylformic acid of table 4. embodiment 7-8 and comparative example C distributes

But the acid of emulsion polymer % copolymerization on particle surface

Embodiment 7 86%

Embodiment 8 22%

Comparative example D 2%

The emulsion polymer particle that the method for embodiment of the invention 7-8 provides comparison to have higher surface acid than embodiment D method.

Embodiment 9. preparations have the emulsion polymer particle on chemical modification surface.Polymeric binder after the shell polymerization, this tackiness agent contains 5% MAA.After the tackiness agent polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1300g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 126.2g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 40g STY, 35.2g MMA and 4.8g MAA, and it is joined in the reactor through 60 minutes at 78 ℃.After adding ME I, with this container of 40gDI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 5gNaDDBS (23%), 558.6g STY and 1.4g allyl methacrylate.From this ME II, take out 115g and place one side.Added ME II through 50 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.After adding ME II, the 40g DI water washing of ME II container.Make reaction mixture be cooled to 85 ℃ and kept 10 minutes.The 3rd monomer emulsion (MEIII) prepares from 100g DI water, 8g NaDDBS (23%), 228g EA and 12g MMA, adds this ME III through 40 minutes in the clockwise reaction mixture.After adding ME III and SPS, with 40g DI water washing container ME III.Add 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene, reaction content was placed 15 minutes.The mixture that adds 3g 5% 4-hydroxyl TEMPO and 10g DI water adds ME II (115g) and the 40g DI water of retaining part then.Adding ammonium hydroxide again (28%, 28.3g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 40g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 30.0%, and pH is 9.6, and particle diameter is 473nm, and S/mil is 0.41.The mensuration dry density is 0.748g/mL.When latex is dry by cast 3.5mil coating on the polyethylene substrate, form the successive film.The mensuration of the film forming minimum temperature of shape (MFFT) shows that MFFT is lower than-5 ℃.

Comparative example E. prepares emulsion polymer particle.Polymer adhesive composition after the shell polymerization does not add MAA in tackiness agent.After the tackiness agent polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1300g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 126.2g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 40g STY, 35.2g MMA and 4.8g MAA, and it is joined in the reactor through 60 minutes at 78 ℃.After adding ME I, with this container of 40gDI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 5gNaDDBS (23%), 558.6g STY and 1.4g allyl methacrylate.From this ME II, take out 115g and place one side.Added ME II through 50 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.After adding ME II, the 40g DI water washing of ME II container.Make reaction mixture be cooled to 85 ℃ and under this temperature, kept 10 minutes.The 3rd monomer emulsion (ME III) prepares from 100g DI water, 8g NaDDBS (23%) and 240g EA, adds this ME III through 40 minutes in the clockwise reaction mixture.After adding ME III and SPS, with 40g DI water washing ME III container.Add 20g 0.1% ferric sulfate and 2g 1% mixture according to ground alkene, reaction content was placed 15 minutes.The mixture that adds 3g 5% 4-hydroxyl TEMPO and 10g DI water adds ME II (115g) and the 40g DI water of retaining part then.Add again ammonium hydroxide (28%, 28.3g), reaction mixture was placed 10 minutes at 85 ℃.Add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water, add the solution of 0.7g IAA in 40g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 30.0%, and pH is 9.8, and particle diameter is 455nm, and S/mil is 0.32.The mensuration dry density is 0.841g/mL.When latex is dry by the wet coating of cast 3.5mil on the polyethylene substrate, finds no film and form.

Comparative example F. prepares emulsion polymer particle.Polymer adhesive composition after the shell polymerization, this tackiness agent contains 5%MAA.After carrying out half, the shell polymerization neutralizes.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1300g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 126.2g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 40g STY, 35.2g MMA and 4.8g MAA, and it is joined in the reactor through 60 minutes at 78 ℃.After adding ME I, with this container of 40gDI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 5gNaDDBS (23%), 558.6g STY and 1.4g allyl methacrylate.Added ME II through 50 minutes in the clockwise reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.When adding half ME II, in reaction mixture, add ammonium hydroxide (28%, 28.3g).After adding ME II, the 40g DI water washing of ME II container.Make reaction mixture be cooled to 85 ℃ and under this temperature, kept 10 minutes.The 3rd monomer emulsion (ME III) prepares from 100g DI water, 8g NaDDBS (23%), 228g EA and 12g MAA, adds this ME III through 40 minutes in the clockwise reaction mixture.After adding ME III and SPS, with 40g DI water washing ME III container.Add 20g 0.1% ferric sulfate and 2g 1% according to the mixture of ground alkene, add 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water again.After adding the solution of 0.7g IAA in 40g DI water, reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 30.0%, and pH is 9.6, and particle diameter is 467nm, and S/mil is 0.32.When latex is dry by cast 3.5mil coating on the polyethylene substrate, do not find to have formed film.

Emulsion polymer by the preparation of the embodiment of the invention 9 methods is not compared with at room temperature there being the film forming comparative example E-F of shape, can be observed lower MFFT, and formed film, show that adhesive polymer layer that the present invention contains soft MAA carries out the effect and the efficient of surface modification.

Embodiment 10. preparations have the emulsion polymer particle on chemical modification surface.By mixing Natvosol is introduced skin with second layer monomer emulsion (ME II).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (2100g), and be heated to 84 ℃.Add the solution of 2.8g SPS in 20g DI water in the water in the reactor of heating.And then add 189.9g nuclear polymer B and 20g DI water.Monomer emulsion (ME I) prepares by mixing 250g DI water, 8g NaDDBS (23%) and 827.4g STY.From this ME I, take out 171g and place one side.79 ℃ of speed initial ME I is partly joined in the reactor with 4.6g/min.After beginning to add ME I, immediately the solution of 12.6g AA in 47.6g DI water is poured in the reaction mixture, after 40 minutes, the adding speed of ME I is increased to 12g/min, and adds the solution of 1.0g SPS in 60gDI water jointly with the speed of 1.0g/min in reactor.The temperature of reactor rises to 92 ℃.After adding ME I, kept 10 minutes at 92 ℃ with 40g DI water washing ME I container and with reaction mixture.The second monomer emulsion (ME II) prepares by 250g DI water, 2g NaDDBS (23%), 18g BA, 40.8g MMA, 1.2g MAA and 19.8g Natvosol (7.5%).Added ME II through 15 minutes in the clockwise reaction mixture.After adding ME II and SPS, the 20g DI water washing of ME II container.The mixture that adds 8g 5%4-hydroxyl TEMPO and 8g DI water adds ME I (171g) and the 20g DI water of retaining then.During adding, reaction mixture is cooled to 85 ℃.Add then ammonium hydroxide (28%, 29.7g).Reaction mixture was placed 5 minutes at 85 ℃, added 8g 0.1% ferric sulfate and 0.8g 1% according to the mixture of ground alkene, added 0.8gSPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water again, and the solution of 0.7g IAA in 40g DI water.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 24.1%, and pH is 9.5, and particle diameter is 690nm.Dry density is determined as 0.573g/mL.After latex is at room temperature placed 3 months, do not find layer or precipitation clearly.

Embodiment 11. preparations have the emulsion polymer particle on chemical modification surface.Natvosol is introduced the second layer (vinylformic acid) of solid polymer particle.After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1700g), and be heated to 85 ℃.Add the solution of 2.8g SPS in 20g DI water in the water in the reactor of heating.And then (44.7% solid is 96nm) with 20g DI water to add 22.1g acrylate copolymer dispersion liquid.Monomer emulsion (ME I) prepares by mixing 250g DI water, 8g NaDDBS (23%) and 814.8gSTY.From this ME I, take out 160g and place one side.Then MAA (25.2g) is joined among the remaining ME I.Through 75 minutes ME I is joined in the reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.After adding ME I, be cooled to 85 ℃ with 40g DI water washing ME I container and with reaction mixture.The second monomer emulsion (ME II) prepares by 250g DI water, 2g NaDDBS (23%), 18g BA, 40.8g MMA, 1.2g MAA and 19.8g Natvosol (7.5%).Added ME II through 15 minutes in the clockwise reactor.After adding ME II and SPS, the 40g DI water washing of ME II container.Add the mixture of 2.0g 1% according to ground alkene and 20.0g 0.1% ferric sulfate, reaction mixture was placed 15 minutes at 85 ℃ then.After adding the mixture of 3g 5%4-hydroxyl TEMPO and 10g DI water, add the ME I (160g) that retains, container 40g DI water washing.Add then ammonium hydroxide (28%, 28.0g).Reaction mixture was placed 10 minutes at 85 ℃, add 0.5g SPS and the solution of 2.0g 70% tertbutyl peroxide in 40g DI water again, add the solution of 0.95g IAA in 20gDI water subsequently, reaction mixture was placed 15 minutes at 85 ℃, be cooled to room temperature then, and remove by filter the condensation product of any formation.The solid content of final latex is 26.9%, and pH is 10.1, and particle diameter is 672nm.After latex is at room temperature placed 3 months, do not find precipitation.

Comparative example G. prepares emulsion polymer particle.Prepare surperficial unmodified polymer dispersion liquid, mix with the hydroxy ethyl fiber cellulose solution then.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.In this reactor, add DI water (1800g), and under nitrogen atmosphere, be heated to 85 ℃.Add the solution of 2.8g SPS in 20g DI water in the water in the reactor of heating.And then add 189.9g nuclear polymer B and 20g DI water.Monomer emulsion (ME) prepares by mixing 250gDI water, 8g NaDDBS (23%) and 887.4g STY.From this ME, take out 168g and place one side.79 ℃ of speed initial ME is partly joined in the reaction mixture with 5.2g/min.After beginning to add ME, immediately the solution of 12.6g AA in 47.4g DI water is poured in the reaction mixture.After 20 minutes, the adding speed of ME is increased to 14g/min, and adds the solution of 1.0g SPS in 60g DI water jointly with the speed of 1g/min in reactor.The temperature of reactor rises to 92 ℃.After adding ME and co-fed SPS, with 40g DI water washing ME container.The mixture that adds 8g 5%4-hydroxyl TEMPO and 8g DI water adds ME I (168g) and the 20g DI water of retaining then.During adding, reaction mixture is cooled to 85 ℃.Add then ammonium hydroxide (28%, 29.7g).Reaction mixture was placed 5 minutes at 85 ℃, added 8g 0.1% ferric sulfate and 0.8g 1% according to the mixture of ground alkene, added 0.8gSPS and 2g 70% tertbutyl peroxide solution and the solution of 0.95g IAA in 20g DI water in 45g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 27.5%, and pH is 9.8, and particle diameter is 510nm.Dry density is determined as 0.739g/mL.

Stir and in the dispersion liquid (88g) of final latex, drip the solution of 0.50g Natvosol (7.5%) down at 11.5g DI water.Stir after 30 minutes, standing mixt, after three days, latex begins sedimentation and clarifying top layer and precipitation occur.

The stability of the emulsion polymer of the Natvosol surface modification that obtains by embodiment of the invention 10-11 method and do not have clarifying layer and sedimentary performance to be better than the emulsion polymer of comparative example G.

Embodiment 12. preparations have the emulsion polymer particle on chemical modification surface.Except retaining the part, methacrylic acid phosphoric acid ethyl ester is positioned at whole shell (ME II).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1500g), and be heated to 82 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY, 44g MMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, container 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 10g NaDDBS (23%), 686g STY and 3.5g linseed oil fatty acid.From this ME II, take out 133g and place one side.Then methacrylic acid etherophosphoric acid (14g) is joined among the remaining ME II, ME II is joined in the reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 1g/min through 60 minutes.The temperature of reactor rises to 92 ℃.After adding ME II and SPS, with 40g DI water washing ME II container.Reaction mixture is cooled to 85 ℃.Add 20g 0.1% ferric sulfate and 2g 1% mixture, and reaction content was placed 15 minutes according to ground alkene.The mixture that adds 5g 5%4-hydroxyl TEMPO and 10gDI water adds ME II (133g) and the 40g DI water of retaining again.(28%, 30.1g), reaction mixture was placed 10 minutes at 85 ℃, added 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water again, added the solution of 0.7g IAA in 40g DI water again to add ammonium hydroxide then.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 27.8%, and pH is 9.6, and particle diameter is 412nm, and S/mil is 0.40.Dry density is determined as 0.856g/mL.

Embodiment 13. preparations have the emulsion polymer particle on chemical modification surface.Except retaining the part, oligomeric acrylic acid is positioned at whole shell (ME II).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (1500g), and be heated to 85 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY, 44g MMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, container 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 10g NaDDBS (23%) and 686g STY.From this ME II, take out 133g and place one side.Be that 1200 oligomeric acrylic acid (50g, 28.8%) joins among the remaining ME II then with molecular-weight average.Through 60 minutes ME II is joined in the reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 1g/min.The temperature of reactor rises to 92 ℃.After adding ME II and SPS, with 40g DI water washing ME II container.Reaction mixture is cooled to 85 ℃.Add 20g 0.1% ferric sulfate and 2g 1% mixture, and reaction content was placed 15 minutes according to ground alkene.The mixture that adds 5g 5%4-hydroxyl TEMPO and 10g DI water adds ME II (133g) and the 40g DI water of retaining then.(28%, 30.1g), reaction mixture was placed 10 minutes at 85 ℃, added 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water again to add ammonium hydroxide subsequently.Add the solution of 0.7g IAA in 20g DI water again.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 27.7%, and pH is 9.6, and particle diameter is 409nm, and S/mil is 0.35.Dry density is determined as 0.834g/mL.

Embodiment 14. preparations have the emulsion polymer particle on chemical modification surface.Oligomeric acrylic acid is positioned at shell (ME III).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.In this reactor, add DI water (1500g), and under nitrogen atmosphere, be heated to 85 ℃.Add the solution of 2.5g SPS in 20g DI water in the water in the reactor of heating.And then add 157.7g nuclear polymer A and 20g DI water.Monomer emulsion (ME I) prepares by mixing 40g DI water, 3g NaDDBS (23%), 50g STY, 44g MMA and 6g MAA, and it is joined in the reactor through 40 minutes at 78 ℃.After adding ME I, container 40g DI water washing.The second monomer emulsion (ME II) prepares by mixing 200g DI water, 8g NaDDBS (23%) and 600g STY.From this ME II, take out 117g and place one side.Through 75 minutes ME II is joined in the reactor, and in reactor, add the solution of 1.0g SPS in 60g DI water jointly with the speed of 0.68g/min.The temperature of reactor rises to 92 ℃.After adding MEII and SPS, with 40g DI water washing ME II container.The 3rd monomer emulsion (ME III) is that 1200 oligomeric acrylic acid (28.8%) prepares by 30g DI water, 3g NaDDBS (23%), 95g MMA and 17.9g molecular-weight average, and joins in the reaction mixture through 15 minutes.Add 20g 0.1% ferric sulfate and 2g 1% mixture, and reaction content was placed 15 minutes according to ground alkene.The mixture that adds 5g 5%4-hydroxyl TEMPO and 10g DI water adds ME II (117g) and the 40g DI water of retaining then.(28%, 26.1g), reaction mixture was placed 10 minutes at 85 ℃, added 0.8g SPS and the solution of 1.5g 70% tertbutyl peroxide in 45g DI water again, added the solution of 0.7g IAA in 20g DI water again to add ammonium hydroxide subsequently.Reaction mixture was placed 15 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 27.2%, and pH is 10.0, and particle diameter is 430nm, and S/mil is 0.40.Dry density is determined as 0.768g/mL.

Embodiment 15. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid (AMPS) is positioned at last 1/3rd of shell (ME II).After the shell polymerization, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (687g), and be heated to 90 ℃.Add the solution of 1.64g SPS in 25g DI water in the water in the reactor of heating.And then add 258.5g nuclear polymer C and 20g DI water.Monomer emulsion (ME I) prepares by mixing 78.5g DI water, 0.53g NaDDBS (in water 23%), 67.3g STY and 10.5g AA, and it is joined in the reactor through 15 minutes at 83 ℃.After adding ME I, container 25g DI water washing.The second monomer emulsion (ME II) prepares by mixing 289g DI water, 3.27g NaDDBS (23%) and 829g STY.From this ME II, take out 64.3g and place one side.Remaining ME II is divided into two portions, 704.6g and 352.3g.AMPS (28.2g, 50% solid) joined in second part of less part (obtain ME III).Through 50 minutes ME II is joined in the reactor, and in reactor, add the solution of 1.96g SPS in 105g DI water jointly with the speed of 1.43g/min.The temperature of reactor rises to 90 ℃.After adding ME II, ME III is joined in the reaction through 25 minutes.What add is last, with 25g DI water washing ME container, and with reaction content placement 5 minutes.Add the solution of 1.7g IAA in 25g DI water, and reaction content was placed 15 minutes.Between resting period, add 33.6g NaDDBS (23%) and the solution of 1.76g linseed oil fatty acid in 131g DI water.Add ME II (64.3g) and the 20g DI water of retaining part then, and reaction mixture was placed 20 minutes.After having placed, add the hot DI water of 1135g, and the temperature of reaction mixture is transferred to 85 ℃.(28%, 35.4g), reaction mixture was placed 20 minutes at 85 ℃ to add ammonium hydroxide then.Add 8.2g 0.1% ferric sulfate and 0.82g 1% mixture according to ground alkene.Common solution and 2.27g IAA the solution in 50g DI water of 3.65g 70% tertbutyl peroxide in 49g DI water that adds through 20 minutes.Reaction mixture was placed 10 minutes at 85 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 25.6%, and particle diameter is 1.14 μ m, and dry density is determined as 0.571g/mL.The titration (with AMBERLITE IRN-150 ion exchange resin treatment after) of deionization latex in water shows that 68% shell acid is titratable, and is positioned at the latex surface.

Embodiment 16. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, Sodium styrene sulfonate (SSS) is positioned at last 1/3rd of shell (ME II).After the shell polymerization, neutralize.

Repeat embodiment 15, except after removing the ME II that retains, SSS being joined among the ME II of second part of smaller portions.That is, behind the taking-up 64.3g ME II, place on one side, remaining ME II is separated into two portions, 704.6g and 352.3g.SSS (14.1g is dissolved in the 42.3gDI water) is joined second part of smaller portions, be called ME III.Add speed and keep identical.The solid content of final latex is 25.3%, and particle diameter is 1.14 μ m, and dry density is determined as 0.542g/mL.The titration (with AMBERLITE IRN-150 ion exchange resin treatment after) of deionization latex in water shows that 56% shell acid is titratable, and is positioned at the latex surface.

Embodiment 17. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, methacrylic acid etherophosphoric acid (PEM) is positioned at last 1/3rd of shell (ME II).After the shell polymerization, neutralize.

Repeat embodiment 15,, PEM is joined among the ME II of second part of smaller portions except after removing the ME II that retains.That is, behind the taking-up 64.3g ME II, place on one side, remaining ME II is separated into two portions, 704.6g and 352.3g.PEM (14.1g) is joined second part of smaller portions, be called ME III.Add speed and keep identical.The solid content of final latex is 25.2%, and particle diameter is 1.15 μ m, and dry density is determined as 0.545g/mL.The titration (with AMBERLITE IRN-150 ion exchange resin treatment after) of deionization latex in water shows that 86% shell acid is titratable, and is positioned at the latex surface.

Embodiment 18. preparations have the emulsion polymer particle on chemical modification surface.Except retaining part, methacrylic acid 2-sulfo group ethyl ester (SEM) is positioned at last 1/3rd of shell (ME II).After the shell polymerization, neutralize.

Repeat embodiment 15,, SEM is joined among the ME II of second part of smaller portions except after removing the ME II that retains.That is, behind the taking-up 64.3g ME II, place on one side, remaining ME II is separated into two portions, 704.6g and 352.3g.SEM (14.1g) is joined second part of smaller portions, be called ME III.Add speed and keep identical.The solids content of final latex is 25.3%, and particle diameter is 1.13 μ m, and dry density is determined as 0.539g/mL.The titration (with AMBERLITE IRN-150 handle back) of deionization latex in water shows that 84% shell acid is titratable, and is positioned at the latex surface.

Embodiment 19. preparations have the emulsion polymer particle on chemical modification surface.Polymerization contains 13.4%N-[3-(dimethylamino) propyl group after the polymerization of vinylbenzene shell] the positively charged ion shell of Methacrylamide (DMAPMA).Before the polymerization of positively charged ion shell, neutralize.

One 5 liter of four neck round-bottomed flask loaded onto paddle stirrer, thermometer, nitrogen inlet and condenser.Under nitrogen atmosphere, in this reactor, add DI water (680g), and be heated to 90 ℃.Add the solution of 1.46g SPS in 22g DI water in the water in the reactor of heating.And then add 229.6g nuclear polymer C and 11g DI water.Monomer emulsion (ME I) prepares by mixing 73.3g DI water, 0.49g NaDDBS (23%), 64.8g MMA, 6.55g BMA and 1.46gMAA, and it is joined in the reactor through 15 minutes at 83 ℃.After adding ME I, container 22g DI water washing.The second monomer emulsion (ME II) prepares by mixing 257g DI water, 2.90g NaDDBS (23%) and 749g STY.From this ME II, take out 57.1g and place one side.Through 80 minutes remaining ME II is joined in the reactor, and in reactor, add the solution of 1.74g SPS in 93.2g DI water jointly with the speed of 1.27g/min.The temperature of reactor rises to 90 ℃.After adding ME II and SPS, with 22g DI water washing ME II container, and with reaction content placement 5 minutes.Add the solution of 1.5g IAA in 22gDI water, and reaction content was placed 15 minutes.Between resting period, add 29.9gNaDDBS (23%) and the solution of 1.56g linseed oil fatty acid in 116g DI water.Add ME II (57.1g) and the 20g DI water of retaining part then, and reaction mixture was placed 20 minutes.After having placed, add the hot DI water of 1400g, and the temperature of reaction mixture is transferred to 85 ℃.(28%, 31.5g), reaction mixture was placed 20 minutes at 85 ℃ to add ammonium hydroxide then.Reaction mixture is cooled to 60 ℃, and adds 14.6g 0.1% ferric sulfate and 1.46g 1% mixture according to ground alkene.The 3rd monomer emulsion (ME III) is from 77.2g DI water, 32gTRITON X-405 (70%), 97.7g EA, 32.1g MMA and 20.1g DMAPMA preparation.Speed with 8.1g/min joins ME III in the reaction mixture, and adds solution and 0.9g IAA the solution in 50g DI water of 1.35g 70% tertbutyl peroxide in 50g DI water jointly with the speed of 1.43g/min in reactor.After adding ME III, with 22gDI water washing ME III container.Common solution and 2.02g IAA the solution in 44.7g DI water of 3.24g 70% tertbutyl peroxide in 43.7g DI water that adds through 20 minutes.Reaction mixture was placed 10 minutes at 60 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solids content of final latex is 24.6%, and dry density is determined as 0.497g/mL.

Embodiment 20. preparations have the emulsion polymer particle on chemical modification surface.Polymerization contains the positively charged ion shell of 20%DMAPMA after the polymerization of vinylbenzene shell.Before the polymerization of positively charged ion shell, neutralize.

Repeat embodiment 19, except the 3rd monomer emulsion (ME III) prepares from 200.6g DI water, 76.8gTRITON X-405 (70%) (TRITON is the trade mark of Union Carbide Corp.), 239.8g STY and 59.9g DMAPMA.Speed with 10.4g/min joins ME III in the reaction mixture, and adds solution and 2.7g IAA the solution in 108g DI water of 4.05g 70% tertbutyl peroxide in 106g DI water jointly with the speed of 2.0g/min in reactor.After adding ME III, with 44g DI water washing ME III container.Common solution and 4.03g IAA the solution in 89.4g DI water of 6.48g 70% tertbutyl peroxide in 87.4g DI water that adds through 20 minutes.Reaction mixture was placed 10 minutes at 60 ℃, was cooled to room temperature then, and removed by filter the condensation product of any formation.The solid content of final latex is 25.0%, and dry density is determined as 0.597g/mL.

Embodiment 21. preparations have the emulsion polymer particle on chemical modification surface.Polymerization contains the shell of 13.4% oxazolidinylethyl methacrylate (OXEMA) after the polymerization of vinylbenzene shell.Before the polymerization of positively charged ion shell, neutralize.

Repeat embodiment 20, except the 3rd monomer emulsion (ME III) prepares from 154.3g DI water, 76.8gTRITON X-405 (70%), 160.3g BA, 48.0g EA and 50.9g OXEMA.The solid content of final latex is 25.0%, and dry density is determined as 0.669g/mL.

Embodiment 22. preparations have the emulsion polymer particle on chemical modification surface.Polymerization contains the shell of 20%OXEMA after the polymerization of vinylbenzene shell.Before the polymerization of positively charged ion shell, neutralize.

Repeat embodiment 20, except the 3rd monomer emulsion (ME III) prepares from 154.3g DI water, 76.8gTRITON X-405 (70%), 149.8g BA, 48.0g EA, 42.0gMMA and 59.9gOXEMA.The solid content of final latex is 25.2%, and dry density is determined as 0.641g/mL.

Claims (11)

1. the method for a chemical modification of polymer particle surface comprises

(a) provide water miscible liquid under the condition of essentially no monomer polymerization, this water miscible liquid contains:

(i) comprise the multistage emulsion polymers of stratum nucleare polymkeric substance and shell polymkeric substance, wherein, described stratum nucleare polymkeric substance contains at least a nonionic monoene that wetting ability monoene as described stratum nucleare polymer weight 5%～100% weight of accounting for of polymerized unit belongs to unsaturated monomer and account for described stratum nucleare polymer weight 0%～95% weight and belongs to unsaturated monomer;

Wherein, the nonionic monoene that contains as at least 50% weight of polymerized unit of described shell polymkeric substance belongs to unsaturated monomer;

(ii) account for the monomer of at least 0.5% weight of described multistage emulsion polymers weight; With

(iii) at least a can with the chemically combined surface modification chemical of described monomer; And

(b) make described monomer content reduce at least 50%.

2. the method for a chemical modification of polymer particle surface comprises

(a) provide water miscible liquid under the condition of essentially no monomer polymerization, this water miscible liquid contains:

(i) comprise the multistage emulsion polymers of stratum nucleare polymkeric substance and shell polymkeric substance; Wherein, at least a nonionic monoene that accounts for stratum nucleare polymer weight 0.1%～100% weight that contains as polymerized unit of described stratum nucleare polymkeric substance belongs to unsaturated monomer;

Wherein, described shell polymkeric substance contains as polymerized unit:

(1) the nonionic monoene that accounts at least 50% weight of described shell polymer weight belongs to unsaturated monomer; And

(2) account at least a surface modification monomer of 0.1%～10% weight of described shell polymer weight;

(ii) account for the monomer of at least 0.5% weight of described multistage emulsion polymers weight; With

(iii) neutralizing agent; And

(b) described monomer content is reduced at least 50%.

3. the method for a chemical modification of polymer particle surface comprises

(a) provide water miscible liquid under the condition of essentially no monomer polymerization, this water miscible liquid contains:

(i) emulsion polymer, this polymkeric substance contain as polymerized unit:

(1) in the weight of described polymkeric substance, the wetting ability monoene of 5%～100% weight belong to unsaturated monomer and

(2) in the weight of described polymkeric substance, at least a nonionic monoene of 0%～95% weight belong to unsaturated monomer and

(ii) in the weight of described emulsion polymer, the monomer of at least 0.5% weight;

(iii) optionally, neutralizing agent; With

(iv) can with the chemically combined at least a surface modification chemical of described monomer; With

(b) make described monomer content reduce at least 50%.

4. claim 1,2 or 3 method comprise that also one or more stoppers that add significant quantity or reductive agent are to stop any step of polymerization basically.

5. the method for claim 4, the add-on of wherein said one or more stoppers or reductive agent in polymer solids, is 25ppm～5,000ppm.

6. the method for claim 4, wherein said one or more stoppers are selected from: N, N-diethyl hydroxylamine, N nitrosodiphenyl amine, 2,4-dinitrophenylhydrazine, Ursol D, thiodiphenylamine, 2,6-dimethyl-octa-2,4,6-triolefin, triethyl-phosphite, 4-nitrosophenol, 2-nitrophenols, p-aminophenol, 4-hydroxyl TEMPO, quinhydrones, to methoxyl group quinhydrones, the tertiary butyl to quinhydrones, 2, the 5-di-t-butyl is to quinhydrones, 1,4-naphthalenediol, 4-tert-butyl catechol, copper sulfate, cupric nitrate, cresols and phenol.

7. claim 1,2 or 3 method, wherein, in the weight of described emulsion polymer, the described monomer of at least 0.5% weight is used to prepare the described monomer of described emulsion polymer for one or more.

8. claim 1,2 or 3 method, wherein, in the weight of described emulsion polymer, the described monomer of at least 0.5% weight is a non-ionic monomer.

9. claim 1,2 or 3 method, wherein said neutralizing agent is selected from volatile alkali, fixed base and composition thereof.

10. claim 1,2 or 3 method wherein, in polymer solids, are brought down below 10,000ppm by the described monomer of polymerization with described monomeric content.

11. emulsion polymer particle with chemical modification surface by claim 1, the preparation of 2 or 3 method.